EP3186309B1 - Primer für klebebänder - Google Patents

Primer für klebebänder Download PDF

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Publication number
EP3186309B1
EP3186309B1 EP15760374.7A EP15760374A EP3186309B1 EP 3186309 B1 EP3186309 B1 EP 3186309B1 EP 15760374 A EP15760374 A EP 15760374A EP 3186309 B1 EP3186309 B1 EP 3186309B1
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EP
European Patent Office
Prior art keywords
primer
epdm
adhesive
ribbed
radical
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German (de)
English (en)
French (fr)
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EP3186309A1 (de
Inventor
Sebastian Dietze
Kai Ellringmann
Marco Kupsky
Duc Hung NGUYEN
Uwe Schümann
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Tesa SE
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Tesa SE
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/057—Metal alcoholates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/02—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving pretreatment of the surfaces to be joined
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B05D3/0254—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L35/02—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L39/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
    • C08L39/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
    • C08L39/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J139/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Adhesives based on derivatives of such polymers
    • C09J139/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
    • C09J139/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2400/00—Presence of inorganic and organic materials
    • C09J2400/10—Presence of inorganic materials
    • C09J2400/16—Metal
    • C09J2400/166—Metal in the pretreated surface to be joined
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2423/00—Presence of polyolefin
    • C09J2423/10—Presence of homo or copolymers of propene
    • C09J2423/108—Presence of homo or copolymers of propene in the pretreated surface to be joined
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2423/00—Presence of polyolefin
    • C09J2423/16—Presence of ethen-propene or ethene-propene-diene copolymers
    • C09J2423/168—Presence of ethen-propene or ethene-propene-diene copolymers in the pretreated surface to be joined
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2425/00—Presence of styrenic polymer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2427/00—Presence of halogenated polymer
    • C09J2427/008—Presence of halogenated polymer in the pretreated surface to be joined
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2433/00—Presence of (meth)acrylic polymer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2433/00—Presence of (meth)acrylic polymer
    • C09J2433/003—Presence of (meth)acrylic polymer in the primer coating
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2455/00—Presence of ABS
    • C09J2455/008—Presence of ABS in the pretreated surface to be joined
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2463/00—Presence of epoxy resin
    • C09J2463/003—Presence of epoxy resin in the primer coating

Definitions

  • the present invention relates to a primer composition for improving the adhesion of adhesive tapes to hard-to-bond substrates, particularly to olefin-based substrates such as PP / EPDM and PP.
  • Primer compositions are disclosed in a variety of patents, but primers are described in only a few writings with which an adhesion improvement of adhesive tapes to be achieved.
  • a primer composition comprising grafted copolymer of an acrylate copolymer grafted with an aminoalkyl group containing terminal primary amino groups, further containing an acrylate copolymer having carboxyl groups in the molecular chain and a solvent.
  • the WO 03/052021 A1 describes a primer composition containing a polydiorganosiloxane polyurea copolymer having electron rich groups and may be in the form of a primer, an adhesive, a pressure-sensitive adhesive or other coating material. This primer composition is also mentioned in connection with adhesive tape applications.
  • EP 739 383 B1 and US 5,602,202 describes primer compositions based on mixtures of styrene / diene block copolymers or styrene / hydrogenated diene block copolymers and selected polyacrylates which are said to improve the adhesion of double-sided pressure-sensitive foamed adhesive tapes to both low-energy and higher-energy surfaces.
  • a primer composition based on a maleated thermoplastic elastomer, a non-halogenated polyolefin and a resin for use as a primer layer within an adhesive tape describes the WO 03/035779 A a primer composition based on a maleated thermoplastic elastomer, a non-halogenated polyolefin and a resin.
  • Other primers are in WO 99/00922 and DE 102011077510 disclosed.
  • Ribbed PP / EPDM proves to be significantly more difficult to bond than plain PP / EPDM in practice.
  • the width of the ribs is normally about 0.8-1.0 mm, wherein the surfaces of the ribs are not completely flat, so that the actual width per rib, to which a flat adhesive tape is in contact, is significantly lower.
  • the number of ribs per cm width is about 5 ribs in common components. Components of the type described are widely used in the automotive industry and there is a need to glue them by means of tape applications on the ribs.
  • a disadvantage of all known primers is further that they do not ensure adequate protection against moisture infiltration and corrosion.
  • moist heat storage or climatic storage under extreme conditions as often required in the automotive, electronics and solar industries, for example, including temperatures of 60 ° C to 90 ° C with a relative humidity of 80% to 90%, it usually comes to humidity immigration.
  • the moisture migrates either between the substrate and the primer or between the primer and the pressure-sensitive adhesive of the adhesive tape or between both.
  • the consequence is that the adhesive tape no longer optimally adheres and can be removed adhesively in an undesired manner.
  • undesirable corrosion can occur, for example, zinc oxide formation under the bond area in the case of galvanized steel as a substrate.
  • the object of the invention is to provide a primer for improving the adhesion of adhesive tapes, in particular adhesive tapes, which contain a foamed or foam-like elastomer layer and which are designed for durable, adhesive bonds.
  • the adhesion should be improved so much that the tapes can be removed after a bonding time of only a few minutes only with their own destruction or destruction of the substrate from the substrate.
  • the effect of improving the adhesion should be achieved both with adhesive tapes based on polyacrylates and with adhesive tapes based on blends of polyacrylates and synthetic rubber (styrene block copolymers).
  • the width of the ribs is usually about 0.8-1.0 mm, wherein the surfaces of the ribs are not completely flat, so that the actual width per rib, to which a flat adhesive tape is in contact, is significantly lower.
  • the number of ribs per cm width is about 5 ribs each.
  • Vinylcaprolactam refers to N-vinylcaprolactam (CAS # 2235-00-9) and "vinylpyrrolidone” N-vinyl-2-pyrrolidone (CAS # 88-12-0).
  • a chlorinated polyolefin in this invention means a polyolefin which has been chlorinated.
  • the polyolefin can be, for example, polypropylene or polyethylene or a copolymer or a blend of polypropylene and polyethylene.
  • the chlorination can be carried out in solvents, dispersions or by the direct action of gaseous chlorine.
  • the CAS no. of chlorinated polypropylene is 68442-33-1.
  • the CAS no. of chlorinated polyethylene is 63231-66-3.
  • a metal acetylacetonate is understood according to the invention to mean a coordination compound of acetylacetonate anions and metal cations.
  • the general formula is: M (acac) m .
  • M stands for a metal cation, acac for the acetylacetonate anion.
  • the IUPAC name for acetylacetone is: pentane-2,4-dione, CAS no. is 123-54-6.
  • the variable m represents the number of acetylacetonate anions required for charge balancing and depends on the oxidation state of the metal cation.
  • metal alkoxide is synonymous with "metal alcoholate”. These are coordination compounds of the general formula: M (OR) n .
  • M stands for a metal cation
  • OR stands for an alcoholate anion.
  • R is an alkyl radical.
  • n stands for the number of alcoholate anions required for charge balancing and depends on the oxidation state of the metal cation.
  • Alkoxy metal acetylacetonates in this document are understood as meaning mixed coordination compounds of both acetylacetonate and alkoxide anions and metal cations.
  • the general formula is M (acac) m (OR) n .
  • M stands for a metal cation
  • acac for the acetylacetonate anion
  • OR for an alcoholate anion.
  • R is an alkyl radical.
  • the variables m and n represent the number of acetylacetonate anions or alcoholate anions required for charge balancing and depend on the oxidation state of the metal cation.
  • primers according to the invention have a strong adhesion both to smooth PP / EPDM and to ribbed PP / EPDM on the one hand and to adhesive tapes both based on polyacrylates and on the basis of blends of polyacrylates and synthetic rubber (styrene block copolymers) on the other hand.
  • PP / EPDM is understood to mean blends (blends) of polypropylene and EPDM.
  • EPDM refers to ethylene-propylene-diene rubber.
  • the adhesion-promoting effect of a primer according to the invention sets in very quickly. It was found that an adhesive tape adhered to the primer layer could no longer be removed without destruction from the primer layer applied to the PP / EPDM surface for a short time after adhering, for example after approximately 3 minutes.
  • a coating material for producing a basecoat Under a primer according to the invention is understood in accordance with DIN EN ISO 4618 a coating material for producing a basecoat.
  • a primer or coating material is applied to the surface of a substrate, followed by film formation by evaporation of the solvent and / or by another chemical or physical curing or film-forming process, and then another, other substance, on the thus produced layer,
  • a paint, a paint, an adhesive or an adhesive tape can be applied.
  • a prerequisite for an adhesion-promoting effect of a primer is that, on the one hand, a good adhesion of the primer layer to the substrate, the surface of which is also referred to as a substrate, is achieved, and, on the other hand, good adherence to the prepared primer layer of the further, other substance to be applied thereto.
  • a primer has an optimum adhesion-promoting effect when it comes to cohesive failure within the fabric, the adhesive product or the adhesive tape or when it comes to destroying the substrate in an attempt to peel off the applied to the primer substance or applied to the primer adhesive product comes on which the primer was previously applied. If the forces required to peel off the primer, adhesive, or tape applied to the primer are higher than they are when no primer is used, adhesion enhancement or adhesion force enhancement is provided. The higher these forces are, the stronger the adhesion improvement or the improvement of the adhesion force.
  • a solvent in the context of the invention is any known liquid which is suitable for dissolving or at least delicately distributing the mixture disclosed in the main claim without having the substances according to the invention of this mixture to enter into an undesirable chemical reaction.
  • Preferred solvents according to the invention are organic solvents, for example esters, ketones, aliphatic or aromatic hydrocarbons and halogenated hydrocarbons. Water and other inorganic solvents are also included within the spirit of the invention.
  • a dispersed mixture is understood according to the invention to mean a finely divided, homogeneous mixture.
  • the degree of the fine distribution and homogeneity is not strictly defined, but it must be sufficient for the formation of a closed layer after coating and the size of the agglomerates or aggregates not dissolved at the molecular level is sufficiently low that the function of the primer layer as, for example, adhesion-promoting layer is ensured.
  • the at least one copolymer of mixture G of the primer according to the invention is preferably a pressure-sensitive adhesive. Particularly preferred are all copolymers contained in the mixture G pressure-sensitive adhesives.
  • a pressure-sensitive adhesive As common in common usage, a substance understood that - especially at room temperature - permanently sticky and sticky. It is characteristic of a pressure-sensitive adhesive that it can be applied by pressure to a substrate and adhere there, whereby the pressure to be applied and the duration of this pressure are not further defined. In some cases, depending on the precise nature of the pressure-sensitive adhesive, the temperature and humidity and the substrate, the effect of a short-term, minimum pressure is sufficient a light touch for a short moment does not go out to obtain the adhesion effect, in other cases, a longer-term exposure time of a high pressure may be necessary.
  • Pressure-sensitive adhesives have special, characteristic viscoelastic properties which lead to permanent tackiness and adhesiveness. Characteristic of them is that when they are mechanically deformed, it comes both to viscous flow processes as well as to build elastic restoring forces. Both processes are in a certain ratio with regard to their respective proportions, depending on the exact composition, the structure and the degree of crosslinking of the pressure-sensitive adhesive as well as on the speed and duration of the deformation and on the temperature.
  • the proportional viscous flow is necessary to achieve adhesion. Only the viscous portions, caused by macromolecules with relatively high mobility, allow a good wetting and a good flow onto the substrate to be bonded. A high proportion of viscous flow leads to a high pressure tack (also referred to as tack or surface tackiness) and thus often also to a high bond strength. Strongly crosslinked systems, crystalline or glassy solidified polymers are usually not or at least only slightly tacky due to the lack of flowable components.
  • the proportional elastic restoring forces are necessary to achieve cohesion. They are caused for example by very long-chained and strongly entangled as well as by physically or chemically crosslinked macromolecules and allow the transmission of forces acting on an adhesive bond forces. They result in an adhesive bond being able to withstand a sustained load acting on it, for example in the form of a permanent shearing load, to a sufficient extent over a relatively long period of time.
  • G ' storage modulus
  • G " loss modulus
  • G " is a measure of the viscous portion of a substance. Both quantities depend on the deformation frequency and the temperature.
  • the sizes can be determined with the help of a rheometer.
  • the material to be examined is exposed to a sinusoidal oscillating shear stress in a plate-and-plate arrangement, for example.
  • shear stress controlled devices the deformation as a function of time and the time lag of this deformation are compared with the introduction of the shear stress measured. This time offset is referred to as the phase angle ⁇ .
  • a substance is generally considered to be pressure-sensitive and is defined as tacky, if at room temperature, here by definition at 23 ° C, in the deformation frequency range of 10 0 to 10 1 rad / sec G 'at least partially in the range of 10 3 bis 10 7 Pa and when G "is also at least in part within this range.” means “in part, that at least a portion of the G 'curve is within the window formed by the deformation of the frequency range including 10 ° up to and including 10 1 rad / sec (abscissa) and the range of G 'values of 10 3 to and including 10 7 Pa (ordinate) is spanned, for G "this applies accordingly.
  • Pressure-sensitive adhesives containing vinylcaprolactam and / or vinylpyrrolidone in the copolymer usually have only average adhesive properties. It was all the more surprising that in the context of the present invention it was found that a primer containing as pressure-sensitive adhesive a copolymer of the invention with vinylcaprolactam and / or vinylpyrrolidone as monomer components has outstanding adhesion-promoting properties and very strong bonding of adhesive tapes to olefin-based substrates, in particular PP / EPDM.
  • the copolymer is particularly preferably a pressure-sensitive adhesive, and the monomer mixture of the copolymer comprises only vinylcaprolactam and / or vinylpyrrolidone and one or more of the monomers a) and / or b), ie the copolymer is composed only of these monomers without containing further copolymerizable monomers are.
  • a primer based on such a copolymer has particularly good adhesion-promoting properties.
  • the presence of other - especially softening - comonomers and components are omitted as the said. For example, it is possible to dispense completely with comonomers with cyclic hydrocarbon building blocks.
  • Linear alkyl esters having 2 to 10 C atoms in the alkyl radical are ethyl acrylate, n-propyl acrylate, n-butyl acrylate, n-pentyl acrylate, n-hexyl acrylate, n-heptyl acrylate, n-octyl acrylate, n-nonyl acrylate, n-decyl acrylate.
  • the monomer mixture contains n-butyl acrylate.
  • Branched non-cyclic acrylic esters having 3 to 12 inclusive carbon atoms in the alkyl radical of the alcohol are preferably selected from the group consisting of 2-ethylhexyl acrylate (EHA), 2-propylheptyl acrylate, isooctyl acrylate, isobutyl acrylate, iso-amyl acrylate and isodecyl acrylate.
  • EHA 2-ethylhexyl acrylate
  • 2-propylheptyl acrylate isooctyl acrylate
  • isobutyl acrylate iso-amyl acrylate
  • isodecyl acrylate Particular preference is given to the monomers b) selected from the group consisting of 2-ethylhexyl acrylate (EHA), 2-propylheptyl acrylate and isooctyl acrylate.
  • Isooctyl acrylate refers to the acrylic acid esters in which the alcohol component is due to a mixture of primary isooctanols, ie to those alcohols which are obtained from an isoheptene mixture by hydroformylation u. subsequent hydrogenation can be obtained.
  • the monomer mixture of the copolymer of the primer according to the invention preferably contains not more than 50% by weight, more preferably not more than 40% by weight, of vinylcaprolactam and / or vinylpyrrolidone, based on the total weight of the monomer mixture.
  • the monomer mixture preferably contains at least 10 wt .-%, particularly preferably at least 20 wt .-%, in particular at least 30 wt .-% vinylcaprolactam and / or vinylpyrrolidone, based on the total weight of the monomer mixture. If vinylcaprolactam and vinylpyrrolidone are present in the monomer mixture, in each case the content of vinylcaprolactam and vinylpyrrolidone in total, ie in total, is meant. Very preferably, the monomer mixture consists of vinylcaprolactam and / or vinylpyrrolidone and exactly one monomer of grade a), particular preference being given to choosing n-butyl acrylate as monomer a).
  • the monomer mixture consists of vinylcaprolactam and n-butyl acrylate.
  • Weight ratio of vinylcaprolactam: n-butyl acrylate preferably from 10:90 to 50:50, more preferably from 20:80 to 40:60.
  • the monomer mixture can contain up to 10% by weight, based on the total weight of the monomer mixture, of further copolymerizable monomers in addition to the monomers already included in the subject of the invention.
  • the other monomers may be selected from the group consisting of: methyl acrylate, methyl methacrylate, ethyl methacrylate, benzyl acrylate, benzyl methacrylate, phenyl acrylate, phenyl methacrylate, isobornyl acrylate, isobornyl methacrylate, t-butylphenyl acrylate, t-butylaphenyl methacrylate, dodecyl methacrylate, lauryl acrylate, n-undecyl acrylate, stearyl acrylate, tridecyl acrylate , Behenyl acrylate, cyclohexyl methacrylate, cyclopentyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, 2-butoxyethyl methacrylate, 2-butoxy-ethyl acrylate, 3,3,5-trimethylcyclo
  • Macromonomers such as 2-polystyrene ethyl methacrylate (molecular weight MW from 4000 to 13000 g / mol), poly (methyl methacrylate) ethyl methacrylate (MW from 2000 to 8000 g / mol).
  • the monomer mixture preferably contains not more than 1% by weight, more preferably not more than 0.1% by weight, based on the total weight of the monomer mixture, of acrylic acid.
  • the monomer mixture is free of acrylic acid.
  • the concentration of the copolymer or the totality of all copolymers of the mixture G, based on the total weight of the primer, is preferably from 1% by weight to 30% by weight, particularly preferably from 2% by weight to 20% by weight, in particular from 3% by weight to 10% by weight.
  • Inventive primers contain at least one chlorinated polyolefin.
  • a chlorinated polyolefin in this invention means a polyolefin which has been chlorinated.
  • the polyolefin can be, for example, polypropylene or polyethylene or a copolymer or a blend of polypropylene and polyethylene.
  • the chlorination can be carried out in solvents, dispersions or by the direct action of gaseous chlorine.
  • the chlorinated polyolefin may be modified to be optionally functionalized with an ⁇ , ⁇ -unsaturated carboxylic acid or its anhydride, especially maleic anhydride, and / or with acrylate monomers in a grafting reaction, the grafting reaction before or after the chlorination can be done.
  • Chlorinated polyolefins are in the primer according to the invention preferably in a proportion of 0.1 to 10 wt .-%, more preferably from 0.5 to 5 wt .-%, in particular from 1 to 2 wt .-%, each based on the total weight of Primers, included.
  • Primers according to the invention comprise at least one metal compound selected from the group consisting of metal acetylacetonates, metal alkoxides and alkoxy-metal acetylacetonates. Synonyms for "alkoxy-metal acetylacetonate" are Metallalkoxidacetylacetonat or Metallacetylacetonatalkoxid. According to the invention, the metal compound may carry further ligands without departing from the spirit of the invention.
  • the metal is preferably selected from the group consisting of titanium, aluminum, zirconium, zinc and iron; In particular, the metal is titanium or zirconium.
  • the metal compound is particularly preferably selected from titanium or zirconium alkoxides. Most preferably, the metal compound is titanium tetraisopropanolate Ti ( i Pr) 4 .
  • the primer according to the invention contains no block copolymers of the polystyrene / polydiene or polystyrene / hydrogenated polydiene type.
  • block copolymers of the polystyrene / polydiene or polystyrene / hydrogenated polydiene type are to be understood as meaning all polymers whose molecules consist of linked blocks of polystyrene and polydiene units or hydrogenated or partially hydrogenated polydiene units or contain such blocks at least substantially .
  • Typical examples of polydiene and hydrogenated or partially hydrogenated polydiene units are polybutadiene, polyisoprene, ethylene / butylene or ethylene / propylene blocks.
  • inventive primers without block copolymers of the polystyrene / polydiene type or polystyrene / hydrogenated polydiene as an additional constituent bring about a further improved adhesion of the bonded adhesive tape to both smooth and ribbed PP / EPDM.
  • the radicals R 1 are preferably, independently of one another, a methyl, ethyl, 2-methoxyethyl or an acetyl radical.
  • the radicals R 3 are independent of one another preferably a methyl, isooctyl, hexadecyl or cyclohexyl radical.
  • the radical R 2 preferably represents an aminoalkyl, glycidoxyalkyl, vinyl, methacryloxymethyl, 3-methacryloxypropyl or a phenyl radical, in particular a 3-glycidoxy- (n-) propyl or an aminoalkyl radical or a vinyl group.
  • the organofunctional silane of the general structure (I) contains an aminoalkyl radical or a vinyl group.
  • the or the organofunctional silane (s) of the general structure (I) is selected from the group consisting of 3-glycidoxypropyltrimethoxysilane (eg GENIOSIL® GF 80, Wacker), 3-glycidoxypropyltriethoxysilane (eg GENIOSIL® GF 82 , Wacker), N-cyclohexylaminomethyl-methyldiethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-phenylaminomethyltrimethoxysilane, N- (2-aminoethyl) -3-amino-propyltrimethoxysilane, N-cyclohexyl-3-aminopropyltrimethoxysilane, N-cycl
  • the primer additionally contains one or more epoxy resins.
  • Epoxy resins here are all uncrosslinked, solid at room temperature or liquid, soluble in suitable solvents, two or more epoxy groups bearing oligomers meant.
  • suitable epoxy resins based on bisphenol A and / or bisphenol F, epoxy phenol novolaks, epoxy cresol novolaks, dicyclopentadiene phenol novolacs, cycloaliphatic epoxy resins, and epoxy resins containing ester or amino groups.
  • the concentration of the sum of the epoxy resins in the primer is preferably at most 12 percent by weight, more preferably at most 6 percent by weight, in particular at most 3 percent by weight, based in each case on the total weight of the primer.
  • the primer additionally contains one or more styrene-acrylate resins.
  • Styrene acrylate resins are understood as meaning all uncrosslinked, solid-state or liquid, room-temperature-soluble resins which are soluble in suitable solvents and comprise at least styrene and also acrylic acid, methacrylic acid, acrylic acid esters and / or Are constructed methacrylic acid esters.
  • Preferred styrene acrylate resins are hydroxyl-containing.
  • the primer additionally contains acetylacetone (CAS No. 123-54-6).
  • concentration of acetylacetone in the primer is preferably greater than 0 to 10.0 wt .-%. Particularly advantageous is a concentration between 0.2 and 5.0 wt .-%.
  • the acetylacetone is advantageously mixed into the mixture G before the addition of the metal acetylacetonates, metal alkoxides or alkoxy-Metallacetylacetonate takes place.
  • a primer according to the invention may comprise further constituents in addition to the abovementioned substances, for example additives such as other polymers, resins, plasticizers, stabilizers, rheological additives, fillers, pigments, crosslinkers, initiators, catalysts, accelerators and the like.
  • additives such as other polymers, resins, plasticizers, stabilizers, rheological additives, fillers, pigments, crosslinkers, initiators, catalysts, accelerators and the like.
  • the primer according to the invention preferably contains one or more fluorescent optical brighteners. This is advantageous because in this way a primed background can be identified. Without optical identification, it is often difficult to distinguish a primed surface from a non-primed surface, since the application rate of a primer is usually very thin and thus optically barely perceptible.
  • a preferred fluorescent optical brightener is 2,5-thiophenediylbis (5-tert-butyl-1,3-benzoxazole), CAS-No. 7128-64-5, commercially available under the trade name Tinopal OB®.
  • the sum of the proportions by weight of mixture G and of the solvents on the primer according to the invention is preferably at least 80%, more preferably at least 85%, in particular at least 90%, for example at least 92% and very particularly preferably at least 95%.
  • a primer according to the invention preferably contains the following components in the stated proportions, in each case based on the total weight of the primer: - copolymer (e) 2 to 9% by weight - Solvents 65 to 95% by weight - chlorinated polyolefin (s) 0.2 to 5% by weight - metal compound (s) 0.2 to 7% by weight - Additives 0.1 to 10% by weight, wherein the proportions add up to 100 wt .-%.
  • Another object of the invention is the use of a primer according to the invention for producing an adhesion-promoting layer, preferably an adhesion-promoting layer in a thickness between 0.1 .mu.m and 10 .mu.m, more preferably an adhesion-promoting layer in a thickness between 1 .mu.m and 5 .mu.m.
  • Another object of the invention is a method for producing an adhesion-promoting layer on a substrate, which comprises applying a primer according to the invention to a substrate and removing the one or more solvents.
  • Primers according to the invention have excellent adhesion to olefin-based substrates, in particular PP / EPDM. They have a strong adhesion to both smooth PP / EPDM and ribbed PP / EPDM on the one hand and to adhesive tapes both based on polyacrylates and on the basis of blends of polyacrylates and synthetic rubber (styrene block copolymers) on the other. They are thus excellent adhesion promoter for bonding of the adhesive tapes mentioned in particular PP / EPDM.
  • adhesion of adhesive tapes is so much improved that the tapes can be removed after a bonding time of only a few minutes only with their own destruction or destruction of the substrate from the substrate.
  • the mentioned effects of adhesion improvement are achieved in particular with adhesive tapes which contain a foamed or foam-like elastomer layer and are designed for durable, adhesive bonds.
  • Ribbed PP / EPDM proves to be significantly more difficult to bond than plain PP / EPDM in practice.
  • the width of the ribs is approximately 0.8-1.0 mm, wherein the surfaces of the ribs are not completely flat, so that the actual width per rib, to which a flat adhesive tape is in contact, is significantly lower.
  • the number of ribs per cm width is about 5 ribs in common components. Components of the type described are widely used in the automotive industry and there is a need to glue them by means of tape applications on the ribs. This can be achieved by mediating liability with the primers according to the invention.
  • the described effect of improving the adhesion of foamed or foam-like adhesive tapes based on polyacrylates or based on blends of polyacrylates and synthetic rubber can also be achieved on untreated polypropylene (PP) in such a way that the adhesive tapes after a bonding time of only a few Minutes can be removed only with their own destruction of the polypropylene.
  • PP polypropylene
  • Olefinbasis such as PP / EPDM and on the other hand on galvanized steel, PP, ABS and PVC can be achieved.
  • the primers according to the invention furthermore ensure good protection against moisture infiltration and corrosion.
  • moisture migrates either between the substrate and the primer or between the primer and the pressure-sensitive adhesive of the adhesive tape or between both.
  • the consequence is that the adhesive tape no longer optimally adheres and can be removed adhesively in an undesired manner.
  • undesirable corrosion for example, to a zinc oxide formation under the Bonding surface in the case of galvanized steel as a substrate.
  • an adhesion-promoting layer with the primer according to the invention is carried out in a known manner, namely by first applying the primer to a substrate. Subsequently, the solvent or solvents are allowed to evaporate, whereupon the adhesive tape can be applied. Between application / evaporation of the solvent and the application of the adhesive tape can be only a few minutes, but also a few days or weeks.
  • Another object of the invention is the use of the primer according to the invention for improving the adhesion of adhesive tapes, in particular adhesive tapes based on polyacrylates or based on blends of polyacrylates and synthetic rubber (styrene block copolymers), on olefin-based substrates, in particular PP / EPDM and PP, more preferably PP / EPDM; and on galvanized steel, ABS and PVC; particularly preferably on olefin-based substrates, in particular on PP / EPDM and PP, very particularly preferably on PP / EPDM.
  • DMA Dynamic mechanical analysis
  • the thickness of the measured pressure-sensitively adhesive copolymer samples was always between 0.9 and 1.1 mm (1 +/- 0.1 mm).
  • the pressure-sensitively adhesive copolymer samples were prepared by spreading the copolymers described below on a double-sided siliconized polyester film (release liner), evaporating off the solvent at 70 ° C. and stacking the resulting 100 ⁇ m thick coatings until a thickness of about 1 mm was reached. Subsequently, the samples to be measured were punched out. The sample diameter was 25 mm in each case. The preload was carried out with a load of 3N. The stress of the specimens was 2500 Pa in all measurements.
  • the bond strength was determined based on PSTC-101 at room temperature.
  • the primer was first applied to the substrate (the substrate) thinly. This was done with a brush spread of the primer on the substrate. After the solvent had evaporated, the adhesive tape to be measured (the adhesive tape) was applied (glued) onto the substrate, which was now provided with the primer in a layer thickness of approximately 1 ⁇ m to 10 ⁇ m.
  • a strip of the adhesive tape in a defined width (standard: 20 mm) was glued to the substrate coated with the primer by rolling over it five times using a 5 kg steel roller.
  • the time between the last roll over of the tape and the peel off was: a) 3 minutes, b) 30 minutes.
  • the take-off angle was 90 °, the take-off speed 300 mm / min.
  • the force required for stripping is the bond strength, which is expressed in units of N / cm and thus refers to a standardized adhesive tape width of 1 cm.
  • the type of failure of the adhesive bond was determined.
  • the measured adhesive strips were back-reinforced with a 23 micron thick, etched with trichloroacetic acid polyester film. All measurements were carried out in an air-conditioned room at 23 ° C and 50% relative humidity.
  • the 23 ⁇ m thick, with trichloroacetic acid etched polyester film back-reinforced samples were subjected to the bond strength test at a take-off angle of 90 ° and a take-off speed of 300 mm / min in an air-conditioned room at 23 ° C and 50% relative humidity.
  • the determination of the static glass transition temperature via differential scanning calorimetry according to DIN 53765.
  • the information on the glass transition temperature T g refer to the glass transition temperature T g according to DIN 53765: 1994-03, unless otherwise indicated in individual cases.
  • Heating curves run at a heating rate of 10 K / min. The samples are measured in AI crucibles with perforated lid and nitrogen atmosphere. The second heating curve is evaluated. A glass transition temperature can be seen as a turning point in the thermogram.
  • the determination of the average molecular weight Mw or the average molecular weight M N and the polydispersity D was carried out by means of gel permeation chromatography (GPC).
  • the eluent used was THF containing 0.1% by volume of trifluoroacetic acid. The measurement was carried out at 25 ° C.
  • PSS-SDV 5 ⁇ m, 10 3 ⁇ (10 -7 m), ID 8.0 mm ⁇ 50 mm was used.
  • the columns were PSS-SDV, 5 ⁇ m, 10 3 ⁇ (10 -7 m), 10 5 ⁇ (10 -5 m) and 10 6 ⁇ (10 -4 m) each having ID 8.0 mm ⁇ 300 mm inserted.
  • the sample concentration was 4 g / l, the flow rate 1.0 ml per minute. It was measured against PMMA standards.
  • the solids content is a measure of the proportion of non-volatile constituents in a polymer solution. It is determined gravimetrically by weighing the solution, then evaporating the vaporizable fractions for 2 hours at 120 ° C in a drying oven and weighing back the residue.
  • test tapes used to test the primer were based on polyacrylate pressure-sensitive adhesives and pressure-sensitive adhesives based on an acrylate / synthetic rubber mixture.
  • the expandability of the microballoons can be described by determining the TMA density [kg / m 3 ] (Stare Thermal Analysis System from Mettler Toledo, heating rate 20 ° C / min).
  • the TMA density is the minimum achievable density at a certain temperature T max under normal pressure before the microballoons collapse.
  • the determination of the softening point of the resins is carried out according to DIN ISO 4625.
  • An exemplary polyacrylate pressure-sensitive adhesive 1 for preparing the test adhesive tape 1 was prepared as follows: A reactor conventional for free-radical polymerizations was reacted with 54.4 kg of 2-ethylhexyl acrylate, 20.0 kg of methyl acrylate, 5.6 kg of acrylic acid and 53.3 kg of acetone. Isopropanol (94: 6) filled. After passing nitrogen gas for 45 minutes with stirring, the reactor was heated to 58 ° C and 40 g of Vazo 67 dissolved in 400 g of acetone was added. Subsequently, the outer heating bath was heated to 75 ° C and the reaction was carried out constantly at this external temperature. After 1 h, 40 g of Vazo 67 dissolved in 400 g of acetone were again added, and after 4 h, the mixture was diluted with 10 kg of acetone / isopropanol mixture (94: 6).
  • This base polymer was melted in a feed extruder (single screw extruder from TROESTER GmbH & Co KG, Germany) and conveyed with this as polymer melt through a heatable hose into a planetary roller extruder from Entex (Bochum).
  • the melted resin Dertophene T 110 was then added via a metering orifice, resulting in a concentration of the resin in the melt of 28.3% by mass.
  • the crosslinker Polypox R16 was added. Its concentration in the melt was 0.14% by mass. All components were mixed to a homogeneous polymer melt.
  • the polymer melt was transferred to a twin-screw extruder (Berstorff). There the accelerator Epikure 925 was added. Its concentration in the melt was 0.14% by mass. Subsequently, the entire polymer mixture was freed in a Vakuumdom at a pressure of 175 mbar of all gas inclusions. Following the vacuum zone, the microballoons were metered in and incorporated homogeneously into the polymer mixture by means of a mixing element. Its concentration in the melt was 0.7% by mass. The resulting melt mixture was transferred to a nozzle.
  • the incorporated microballoons expanded, whereby the pressure drop resulted in a shear-free cooling of the polymer mass.
  • the result was a foamed polyacrylate pressure-sensitive adhesive, which was then formed by means of a roll calender web-shaped in a thickness of 0.8 mm and covered with a double-sided siliconized release film (50 micron polyester), during which the chemical crosslinking reaction progressed.
  • the wound film was stored at room temperature for four weeks before being further used for the primer test.
  • the wound film is the test adhesive tape 1 .
  • Test Tape 2 (three-layer acrylic tape)
  • An exemplary polyacrylate pressure-sensitive adhesive 2A for producing the middle layer of the three-layer test adhesive tape 2 was prepared as follows:
  • a conventional reactor for radical polymerizations was charged with 30.0 kg of 2-ethylhexyl acrylate, 67.0 kg of butyl acrylate, 3.0 kg of acrylic acid and 66.7 kg of acetone / isopropanol (96: 4). After passage of nitrogen gas for 45 minutes with stirring, the reactor was heated to 58 ° C. and 50 g of Vazo 67 dissolved in 500 g of acetone were added. Subsequently, the outer heating bath was heated to 70 ° C and the reaction was carried out constantly at this external temperature.
  • This base polymer was melted in a feed extruder (single screw extruder from TROESTER GmbH & Co KG, Germany) and conveyed with this as polymer melt through a heatable hose into a planetary roller extruder from Entex (Bochum).
  • the crosslinker Polypox R16 has now been added via a metering opening. Its concentration in the melt was 0.22% by mass. All components were mixed to a homogeneous polymer melt.
  • the polymer melt was transferred to a twin-screw extruder (Berstorff). There the accelerator Epikure 925 was added. Its concentration in the melt was 0.14% by mass. Subsequently, the entire polymer mixture was freed in a Vakuumdom at a pressure of 175 mbar of all gas inclusions. Following the vacuum zone, the microballoons were metered in and incorporated homogeneously into the polymer mixture by means of a mixing element. Its concentration in the melt was 2.0% by mass. The resulting melt mixture was transferred to a nozzle.
  • the foamed polyacrylate pressure-sensitive adhesive 2A which was then formed by means of a roll calender web-shaped in a thickness of 0.8 mm and covered with a double-sided siliconized release film (50 micron polyester), while the chemical crosslinking reaction progressed.
  • the wound film was stored for one day at room temperature prior to further processing (see below).
  • An exemplary polvacrylate pressure-sensitive adhesive 2B for the preparation of the two outer layers of the three-layer test adhesive tape 2 was prepared as follows: A conventional 100 L glass reactor for free-radical polymerizations was charged with 4.8 kg of acrylic acid, 11.6 kg of butyl acrylate, 23.6 kg of 2-ethylhexyl acrylate and 26.7 kg of acetone / special gasoline 60/95 (1: 1). After passing nitrogen gas with stirring for 45 minutes, the reactor was heated to 58 ° C and 30 g of AIBN was added. Subsequently, the outer heating bath was heated to 75 ° C and the reaction was carried out constantly at this external temperature. After 1 h of reaction time, 30 g of AIBN were again added.
  • a film of the polyacrylate pressure-sensitive adhesive 2B was laminated on both sides.
  • the two-sided siliconized release film of the foamed polyacrylate pressure-sensitive adhesive 2A uncovered.
  • one of the two-sided siliconized release films of the two foamed polyacrylate pressure-sensitive adhesives 2B was also covered.
  • the 3-layer composite of polyacrylate pressure sensitive adhesive 2B / polyacrylate pressure sensitive adhesive 2A / polyacrylate pressure sensitive adhesive 2B was wound up and stored for four weeks at room temperature before further use for the primer test. The wound composite is the test adhesive tape 2 .
  • An exemplary polyacrylate pressure-sensitive adhesive 3 for the preparation of the test adhesive tape 3 was produced as follows: A reactor conventional for radical polymerizations was charged with 72.0 kg of 2-ethylhexyl acrylate, 20.0 kg of methyl acrylate, 8.0 kg of acrylic acid and 66.6 kg of acetone / isopropanol (94: 6). After passing nitrogen gas for 45 minutes with stirring, the reactor was heated to 58 ° C and 50 g of AIBN dissolved in 500 g of acetone was added. Subsequently, the outer heating bath was heated to 75 ° C and the reaction was carried out constantly at this external temperature. After 1 h, 50 g of AIBN dissolved in 500 g of acetone were again added and after 4 h, diluted with 10 kg of acetone / isopropanol mixture (94: 6).
  • the mixture with the synthetic rubber was prepared as follows: In a planetary roller extruder, the synthetic rubber Kraton D1118 was melted as granules via a solids meter. This was followed by the addition of a microballoon paste (50% Expancel 051DU40 in Ethomeen C25). Via a sidefeeder, the polyacrylate base polymer was added, which was pre-melted in a single-screw extruder, and a terpene phenolic resin (Dertophen DT105) added. Crosslinker (Polypox R16 15% in Rheofos RDP) and accelerator (15% Epicure 925 in Rheofos RDP) solution were added to the mixture.
  • the melt was mixed and coated via a two-roll calender between two release films (siliconized PET film). This resulted in a single-layer adhesive tape with a layer thickness of 1000 microns and a density of 550 kg / m 3 .
  • This adhesive tape is the test tape 3 .
  • polyacrylate pressure-sensitive adhesives for use as a component in the primer according to the invention were prepared as follows:
  • a conventional 100 L glass reactor for free-radical polymerizations was charged with 12.0 kg of N-vinylcaprolactam, 28.0 kg of n-butyl acrylate and 26.7 kg of acetone / special gasoline 60/95 (1: 1). After passing nitrogen gas with stirring for 45 minutes, the reactor was heated to 58 ° C and 30 g of AIBN was added. Subsequently, the outer heating bath was heated to 75 ° C and the reaction was carried out constantly at this external temperature. After 1 h of reaction time, 30 g of AIBN were again added. After 4 and 8 h was diluted with 10.0 kg of acetone / special gasoline 60/95 (1: 1) mixture.
  • a conventional 100 L glass reactor for free-radical polymerizations was charged with 8.0 kg of N-vinylcaprolactam, 32.0 kg of 2-ethylhexyl acrylate and 26.7 kg of acetone / special gasoline 60/95 (1: 1). After passing nitrogen gas with stirring for 45 minutes, the reactor was heated to 58 ° C and 30 g of AIBN was added. Subsequently, the outer heating bath was heated to 75 ° C and the reaction was carried out constantly at this external temperature. After 1 h of reaction time, 30 g of AIBN were again added. After 4 and 8 h was diluted with 10.0 kg of acetone / special gasoline 60/95 (1: 1) mixture.
  • a conventional 100 L glass reactor for free-radical polymerizations was charged with 8.0 kg of N-vinyl-2-pyrrolidone, 32 kg of butyl acrylate, and 26.7 kg of acetone / special gasoline 60/95 (1: 1). After passing nitrogen gas with stirring for 45 minutes, the reactor was heated to 58 ° C and 30 g of AIBN was added. Subsequently, the outer heating bath was heated to 75 ° C and the reaction was carried out constantly at this external temperature. After 1 h of reaction time, 30 g of AIBN were again added. After 4 and 8 h was diluted with 10.0 kg of acetone / special gasoline 60/95 (1: 1) mixture.
  • a conventional 100 L glass reactor for free-radical polymerizations was charged with 15.4 kg of butyl acrylate, 24.4 kg of 2-ethylhexyl acrylate and 26.7 kg of acetone / special gasoline 60/95 (1: 1). After passing nitrogen gas with stirring for 45 minutes, the reactor was heated to 58 ° C and 30 g of AIBN was added. Subsequently, the outer heating bath was heated to 75 ° C and the reaction was carried out constantly at this external temperature. After 1 h of reaction time, 30 g of AIBN were again added. After 4 and 8 h was diluted with 10.0 kg of acetone / special gasoline 60/95 (1: 1) mixture.
  • Primer adhesives 1 to 4 were briefly characterized by DMA measurements.
  • the G 'and G "curves of the primer pressure-sensitive adhesives 1 to 4 were always in the deformation frequency range of 10 ° to 10 1 rad / sec at 23 ° C, at least in part in the range of 10 3 to 10 7 Pa.
  • the primer pressure-sensitive adhesives described above with regard to their preparation and composition were used, as well as the following raw materials: Chemical compound / description (manufacturer's information) trade name Manufacturer or supplier CAS-No.
  • the primers according to the invention were modified with the following raw materials: Chemical compound / description (manufacturer's information) trade name Manufacturer or supplier SBS block copolymer Kraton® D 1102 E Kraton Polymers Hydrogenated SEBS block copolymer Kraton® G 1652 E Kraton Polymers
  • fluorescent optical brightener Chemical compound / description (manufacturer's information) trade name Manufacturer or supplier CAS-No. 2,5-Thiophendiylbis (5-tert-butyl-1,3-benzoxazole) Tinopal OB® BASF 7128-64-5
  • the raw materials / components given in the examples were mixed with a laboratory stirrer from IKA® using a propeller stirrer for about two hours. First, the solvents were mixed, respectively, then the chlorinated polyolefin was dissolved therein by stirring for about one hour. The others Raw materials were then added individually. In those examples in which acetylacetone was used, its addition and stirring took place immediately following the dissolution of the chlorinated polyolefin.
  • composition of the primer is composition of the primer:
  • test tape substratum Adhesive force 300mm / min
  • N / cm Adhesive strength after climatic storage
  • composition of the primer Raw material / component weight Primer pressure sensitive adhesive 2 (40 weight percent solids) 10.40 Hardlen DX 526 P 1.50 Tyzor TPT 0.50 solvent cyclohexane 41.10 xylene 19,70 ethylbenzene 5.00 acetone 7.00 petrol 3.70 isopropanol 9.10 ethyl acetate 2.00 Total 100.00
  • test tape substratum Adhesive force 300mm / min
  • N / cm Adhesive strength after climatic storage
  • composition of the primer Raw material / component weight Primer pressure-sensitive adhesive 1 (40 weight percent solids) 10.40 Hardlen DX 526 P 1.50 Tyzor TnBT 0.50 solvent cyclohexane 41.10 xylene 19,70 ethylbenzene 5.00 acetone 7.00 petrol 3.70 isopropanol 9.10 ethyl acetate 2.00 Total 100.00
  • test tape substratum Adhesive force 300mm / min
  • N / cm Adhesive strength after climatic storage
  • composition of the primer Raw material / component weight Primer pressure-sensitive adhesive 1 (40 weight percent solids) 10.40 Hardlen DX 526 P 1.50 Tyzor TPT 1.00 Geniosil GF 80 0.50 solvent cyclohexane 40,10 xylene 19,70 ethylbenzene 5.00 acetone 7.00 petrol 3.70 isopropanol 9.10 ethyl acetate 2.00 Total 100.00
  • test tape substratum Adhesive force 300mm / min
  • N / cm Adhesive strength after climatic storage
  • composition of the primer Raw material / component weight Primer pressure-sensitive adhesive 1 (40 weight percent solids) 10.40 Hardlen DX 526 P 1.50 Tyzor TnBT 1.00 Geniosil GF 80 0.50 solvent cyclohexane 40,10 xylene 19,70 ethylbenzene 5.00 acetone 7.00 petrol 3.70 isopropanol 9.10 ethyl acetate 2.00 Total 100.00
  • test tape substratum Adhesive force 300mm / min
  • N / cm Adhesive strength after climatic storage
  • composition of the primer Raw material / component weight Primer pressure-sensitive adhesive 1 (40 weight percent solids) 10.40 Hardlen F6 P 1.50 Tyzor TPT 0.50 acetylacetone 0.50 solvent cyclohexane 40.60 xylene 19,70 ethylbenzene 5.00 acetone 7.00 petrol 3.70 isopropanol 9.10 ethyl acetate 2.00 Total 100.00
  • test tape substratum Adhesive force 300mm / min
  • N / cm Adhesive strength after climatic storage
  • composition of the primer Raw material / component weight Primer pressure-sensitive adhesive 1 (40 weight percent solids) 10.40 Hardlen F6 P 1.50 Tyzor TPT 0.50 Geniosil GF 80 0.50 acetylacetone 0.50 solvent cyclohexane 40,10 xylene 19,70 ethylbenzene 5.00 acetone 7.00 petrol 3.70 isopropanol 9.10 ethyl acetate 2.00 Total 100.00
  • test tape substratum Adhesive force 300mm / min
  • N / cm Adhesive strength after climatic storage
  • composition of the primer Raw material / component weight Primer pressure-sensitive adhesive 1 (40 weight percent solids) 10.40 Hardlen F6 P 1.50 Tyzor TPT 0.50 Geniosil GF 80 0.50 Desmophen A 365 2.60 acetylacetone 0.50 solvent cyclohexane 37.50 xylene 19,70 ethylbenzene 5.00 acetone 7.00 petrol 3.70 isopropanol 9.10 ethyl acetate 2.00 Total 100.00
  • test tape substratum Adhesive force 300mm / min
  • N / cm Adhesive strength after climatic storage
  • composition of the primer Raw material / component weight Primer pressure-sensitive adhesive 1 (40 weight percent solids) 10.40 Hardlen F6 P 1.50 Tyzor TPT 0.50 Geniosil GF 80 0.50 Desmophen A 365 2.60 Epicote 828 0.20 acetylacetone 0.50 Tinopal OB 0.15 solvent cyclohexane 37.15 xylene 19,70 ethylbenzene 5.00 acetone 7.00 petrol 3.70 isopropanol 9.10 ethyl acetate 2.00 Total 100.00
  • test tape substratum Adhesive force 300mm / min
  • N / cm Adhesive strength after climatic storage
  • composition of the primer Raw material / component weight Primer pressure-sensitive adhesive 1 (40 weight percent solids) 10.40 Hardlen F6 P 1.50 Tyzor TPT 2.00 Geniosil GF 80 1.00 Desmophen A 365 2.60 Epicote 828 0.20 acetylacetone 1.00 Tinopal OB 0.15 solvent cyclohexane 35,00 xylene 19,70 ethylbenzene 5.00 acetone 6.65 petrol 3.70 isopropanol 9.10 ethyl acetate 2.00 Total 100.00
  • test tape substratum Adhesive force 300mm / min
  • N / cm Adhesive strength after climatic storage
  • composition of the primer Raw material / component weight Primer pressure sensitive adhesive 2 (40 weight percent solids) 10.40 Hardlen F6 P 1.50 Tyzor TPT 0.50 Geniosil GF 80 0.50 Desmophen A 365 2.60 Epicote 828 0.20 acetylacetone 0.50 Tinopal OB 0.15 solvent cyclohexane 37.15 xylene 19,70 ethylbenzene 5.00 acetone 7.00 petrol 3.70 isopropanol 9.10 ethyl acetate 2.00 Total 100.00
  • test tape substratum Adhesive force 300mm / min
  • N / cm Adhesive strength after climatic storage
  • climate change 1 (single-layer AC) 1 (PP / EPDM smooth) 59.8 (K) 63.1 (K) nb nb 1 2 (PP / EPDM ribbed) 6.2 (K) 6.4 (K) nb nb 1 3 (PP / EPDM ribbed) 6.1 (K) 6.8 (K) nb nb 1 4 (PP / EPDM ribbed) 6.2 (K) 6,7 (K) nb nb 1 5 (PP) nb nb nb nb 1 6 (hot-dip galvanized steel) nb nb nb nb 1 7 (ABS) nb nb nb nb 1 8 (PVC) nb nb nb nb 3 (single-layer AC / SBS) 1 (PP / EPDM smooth) 62.1 (K) 65.6 (K) nb nb 3 2 (PP / EPDM ribbed)
  • composition of the primer Raw material / component weight Primer pressure sensitive adhesive 3 (40 weight percent solids) 10.40 Hardlen F6 P 1.50 Tyzor TPT 0.50 Geniosil GF 80 0.50 Desmophen A 365 2.60 Epicote 828 0.20 acetylacetone 0.50 Tinopal OB 0.15 solvent cyclohexane 37.15 xylene 19,70 ethylbenzene 5.00 acetone 7.00 petrol 3.70 isopropanol 9.10 ethyl acetate 2.00 Total 100.00
  • test tape substratum Adhesive force 300mm / min
  • N / cm Adhesive strength after climatic storage
  • composition of the primer Raw material / component weight Primer pressure-sensitive adhesive 1 (40 weight percent solids) 10.40 Hardlen F6 P 1.50 Tyzor TnBT 0.50 Geniosil GF 80 0.50 Desmophen A 365 2.60 Epicote 828 0.20 acetylacetone 0.50 solvent cyclohexane 37.30 xylene 19,70 ethylbenzene 5.00 acetone 7.00 petrol 3.70 isopropanol 9.10 ethyl acetate 2.00 Total 100.00
  • test tape substratum Adhesive force 300mm / min
  • N / cm Adhesive strength after climatic storage
  • composition of the primer Raw material / component weight Primer pressure-sensitive adhesive 1 (40 weight percent solids) 10.40 Hardlen F6 P 1.50 Tyzor AA-95 0.50 Geniosil GF 80 0.50 Desmophen A 365 2.60 Epicote 828 0.20 acetylacetone 0.50 solvent cyclohexane 37.30 xylene 19,70 ethylbenzene 5.00 acetone 7.00 petrol 3.70 isopropanol 9.10 ethyl acetate 2.00 Total 100.00
  • test tape substratum Adhesive force 300mm / min
  • N / cm Adhesive strength after climatic storage
  • composition of the primer Raw material / component weight Primer pressure-sensitive adhesive 1 (40 weight percent solids) 10.40 Hardlen F6 P 1.50 Tyzor NBZ 0.50 Geniosil GF 80 0.50 Desmophen A 365 2.60 Epicote 828 0.20 acetylacetone 0.50 solvent cyclohexane 37.30 xylene 19,70 ethylbenzene 5.00 acetone 7.00 petrol 3.70 isopropanol 9.10 ethyl acetate 2.00 Total 100.00
  • test tape substratum Adhesive force 300mm / min
  • N / cm Adhesive strength after climatic storage
  • composition of the primer Raw material / component weight Primer pressure-sensitive adhesive 1 (40 weight percent solids) 10.40 Hardlen F6 P 1.50 Tyzor TPT 0.50 Geniosil XL 10 0.50 Desmophen A 365 2.60 Epicote 828 0.20 acetylacetone 0.50 solvent cyclohexane 37.30 xylene 19,70 ethylbenzene 5.00 acetone 7.00 petrol 3.70 isopropanol 9.10 ethyl acetate 2.00 Total 100.00
  • test tape substratum Adhesive force 300mm / min
  • N / cm Adhesive strength after climatic storage
  • composition of the comparative primer Raw material / component weight Primer pressure sensitive adhesive 4 (40 weight percent solids) 10.40 Hardlen DX 526 P 1.50 Tyzor TPT 0.50 solvent cyclohexane 41.10 xylene 19,70 ethylbenzene 5.00 acetone 7.00 petrol 3.70 isopropanol 9.10 ethyl acetate 2.00 Total 100.00
  • composition of the comparative primer Raw material / component weight Primer pressure sensitive adhesive 4 (40 weight percent solids) 10.40 Hardlen F6 P 1.50 Tyzor TnBT 0.50 solvent cyclohexane 41.10 xylene 19,70 ethylbenzene 5.00 acetone 7.00 petrol 3.70 isopropanol 9.10 ethyl acetate 2.00 Total 100.00
  • composition of the primer Raw material / component weight Primer pressure-sensitive adhesive 1 (40 weight percent solids) 10.40 Hardlen DX 526 P 1.50 Tyzor TPT 0.50 Kraton® D 1102 E 0.50 solvent cyclohexane 40.60 xylene 19,70 ethylbenzene 5.00 acetone 7.00 petrol 3.70 isopropanol 9.10 ethyl acetate 2.00 Total 100.00
  • test tape substratum Adhesive force 300mm / min) (N / cm) after 3 min after 30 min after 24 hours 1 (single-layer AC) 1 (PP / EPDM smooth) 21.4 (A) 23.6 (A) 24.1 (A) 1 2 (PP / EPDM ribbed) 2,3 (A) 3.2 (A) 3.7 (A) 1 3 (PP / EPDM ribbed) 2.2 (A) 2.9 (A) 3.0 (A) 1 4 (PP / EPDM ribbed) 2.4 (A) 2.8 (A) 3.0 (A) 3 (single-layer AC / SBS) 1 (PP / EPDM smooth) 24.2 (A) 25.8 (A) 26.8 (A) 3 2 (PP / EPDM ribbed) 2.2 (A) 2.6 (A) 3.2 (A) 3 3 (PP / EPDM ribbed) 2,3 (A) 3.1 (A) 3.2 (A) 3
  • composition of the primer Raw material / component weight Primer pressure-sensitive adhesive 1 (40 weight percent solids) 10.40 Hardlen DX 526 P 1.50 Tyzor TPT 0.50 Kraton® G 1652 E 0.50 solvent cyclohexane 40.60 xylene 19,70 ethylbenzene 5.00 acetone 7.00 petrol 3.70 isopropanol 9.10 ethyl acetate 2.00 Total 100.00
  • test tape substratum Adhesive force 300mm / min) (N / cm) after 3 min after 30 min after 24 hours 1 (single-layer AC) 1 (PP / EPDM smooth) 22.2 (A) 23.8 (A) 24.6 (A) 1 2 (PP / EPDM ribbed) 2.4 (A) 2.6 (A) 2,7 (A) 1 3 (PP / EPDM ribbed) 2,3 (A) 2.9 (A) 3.1 (A) 1 4 (PP / EPDM ribbed) 2.4 (A) 2.6 (A) 3.9 (A) 3 (single-layer AC / SBS) 1 (PP / EPDM smooth) 23.9 (A) 25.2 (A) 25.8 (A) 3 2 (PP / EPDM ribbed) 2.4 (A) 2,7 (A) 3.0 (A) 3 3 (PP / EPDM ribbed) 2.4 (A) 3.0 (A) 3.1 (A) 3 4
  • composition of the primer Raw material / component weight Primer pressure-sensitive adhesive 1 (40 weight percent solids) 10.40 Hardlen F6 P 1.50 Tyzor TPT 0.50 Kraton® D 1102 E 0.50 Geniosil GF 80 0.50 Desmophen A 365 2.60 Epicote 828 0.20 acetylacetone 0.50 Tinopal OB 0.15 solvent cyclohexane 36.65 xylene 19,70 ethylbenzene 5.00 acetone 7.00 petrol 3.70 isopropanol 9.10 ethyl acetate 2.00 Total 100.00
  • test tape substratum Adhesive force 300mm / min) (N / cm) after 3 min after 30 min after 24 hours 1 (single-layer AC) 1 (PP / EPDM smooth) 25.7 (A) 28.2 (A) 28.9 (A) 1 2 (PP / EPDM ribbed) 3.0 (A) 3.3 (A) 3.6 (A) 1 3 (PP / EPDM ribbed) 3.1 (A) 3.2 (A) 3.7 (A) 1 4 (PP / EPDM ribbed) 3.2 (A) 3.8 (A) 4.0 (A) 3 (single-layer AC / SBS) 1 (PP / EPDM smooth) 24.9 (A) 26.3 (A) 26.9 (A) 3 2 (PP / EPDM ribbed) 2.6 (A) 2.6 (A) 3.1 (A) 3 3 (PP / EPDM ribbed) 2,7 (A) 3.0 (A) 3.2 (A)
  • composition of the primer Raw material / component weight Primer pressure-sensitive adhesive 1 (40 weight percent solids) 10.40 Hardlen F6 P 1.50 Tyzor TPT 0.50 Kraton® G 1652 E 0.50 Geniosil GF 80 0.50 Desmophen A 365 2.60 Epicote 828 0.20 acetylacetone 0.50 Tinopal OB 0.15 solvent cyclohexane 36.65 xylene 19,70 ethylbenzene 5.00 acetone 7.00 petrol 3.70 isopropanol 9.10 ethyl acetate 2.00 Total 100.00
  • test tape substratum Adhesive force 300mm / min) (N / cm) after 3 min after 30 min after 24 hours
  • 1 (single-layer AC) 1 (PP / EPDM smooth) 25.3 (A) 27.8 (A) 27.9 (A) 1 2 (PP / EPDM ribbed) 2.0 (A) 3.6 (A) 3.8 (A) 1 3 (PP / EPDM ribbed) 2.9 (A) 2.9 (A) 3.2 (A) 1 4 (PP / EPDM ribbed) 2.6 (A) 2.9 (A) 3.6 (A) 3 (single-layer AC / SBS) 1 (PP / EPDM smooth) 25.1 (A) 26.7 (A) 27.8 (A) 3 2 (PP / EPDM ribbed) 2.4 (A) 2.9 (A) 3.6 (A) 3 3 (PP / EPDM ribbed) 2.6 (A) 3.0 (A) 3.1 (A) 3
  • test tape substratum Adhesive force 300mm / min) (N / cm) after 3 min after 30 min after 24 hours
  • 1 (single-layer AC) 1 (PP / EPDM smooth) 25.3 (A) 27.8 (A) 27.9 (A) 1 2 (PP / EPDM ribbed) 2.0 (A) 3.6 (A) 3.8 (A) 1 3 (PP / EPDM ribbed) 2.9 (A) 2.9 (A) 3.2 (A) 1 4 (PP / EPDM ribbed) 2.6 (A) 2.9 (A) 3.6 (A) 3 (single-layer AC / SBS) 1 (PP / EPDM smooth) 25.1 (A) 26.7 (A) 27.8 (A) 3 2 (PP / EPDM ribbed) 2.4 (A) 2.9 (A) 3.6 (A) 3 3 (PP / EPDM ribbed) 2.6 (A) 3.0 (A) 3.1 (A) 3

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)
  • Paints Or Removers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
EP15760374.7A 2014-08-29 2015-08-27 Primer für klebebänder Active EP3186309B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102014217245.4A DE102014217245A1 (de) 2014-08-29 2014-08-29 Primer für Klebebänder
PCT/EP2015/001749 WO2016030017A1 (de) 2014-08-29 2015-08-27 Primer für klebebänder

Publications (2)

Publication Number Publication Date
EP3186309A1 EP3186309A1 (de) 2017-07-05
EP3186309B1 true EP3186309B1 (de) 2019-02-27

Family

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EP15760374.7A Active EP3186309B1 (de) 2014-08-29 2015-08-27 Primer für klebebänder

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Country Link
US (1) US10513634B2 (zh)
EP (1) EP3186309B1 (zh)
JP (1) JP2017532403A (zh)
KR (1) KR102009013B1 (zh)
CN (1) CN106661409B (zh)
BR (1) BR112017002560A2 (zh)
CA (1) CA2954937A1 (zh)
DE (1) DE102014217245A1 (zh)
ES (1) ES2724359T3 (zh)
MX (1) MX2017001786A (zh)
TW (1) TWI658105B (zh)
WO (1) WO2016030017A1 (zh)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102016210536A1 (de) * 2016-04-13 2017-10-19 Tesa Se Einfärbbarer Primer
DE102016212508A1 (de) * 2016-07-08 2018-01-11 Tesa Se Härtbare Klebemasse und darauf basierende Reaktivklebebänder

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69409548T2 (de) 1994-01-14 1998-08-27 Minnesota Mining & Mfg Acrylat enthaltende polymermischungen
US5602202A (en) 1994-01-14 1997-02-11 Minnesota Mining And Manufacturing Company Methods of using acrylate-containing polymer blends
CN1188500A (zh) * 1995-06-22 1998-07-22 美国3M公司 使用含丙烯酸酯的聚合物共混物的方法
US5605964A (en) 1995-06-22 1997-02-25 Minnesota Mining And Manufacturing Company Acrylate-containing polymer blends and methods of using
US5623010A (en) 1995-06-22 1997-04-22 Minnesota Mining And Manufacturing Company Acrylate-containing polymer blends and methods of using
JP4856322B2 (ja) 2001-06-08 2012-01-18 スリーエム イノベイティブ プロパティズ カンパニー 塗装板用プライマー組成物
US20030152767A1 (en) 2001-10-22 2003-08-14 3M Innovative Properties Company Polyolefin pressure sensitive adhesive tape with an improved priming layer
US7090922B2 (en) 2001-12-18 2006-08-15 3M Innovative Properties Company Silicone priming compositions, articles, and methods
JP2008156566A (ja) 2006-12-26 2008-07-10 Three M Innovative Properties Co プライマー組成物及び該プライマー組成物を用いた粘着テープ
JP2008184542A (ja) 2007-01-30 2008-08-14 Three M Innovative Properties Co プライマ組成物及び接着性基材
DE102010062669A1 (de) 2010-12-08 2012-06-14 Tesa Se Verfahren zur Herstellung geschäumter Polymermassen, geschäumte Polymermassen und Klebeband damit
DE102011077510A1 (de) 2011-06-14 2012-12-20 Tesa Se Primer zur Verbesserung der Adhäsion von Klebebändern auf schwer verklebbaren Kunststoffen und Metallen
EP2581423A1 (en) * 2011-10-14 2013-04-17 3M Innovative Properties Company Primerless multilayer adhesive film for bonding glass substrates

Non-Patent Citations (1)

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Title
None *

Also Published As

Publication number Publication date
EP3186309A1 (de) 2017-07-05
WO2016030017A1 (de) 2016-03-03
CN106661409B (zh) 2019-04-12
JP2017532403A (ja) 2017-11-02
ES2724359T3 (es) 2019-09-10
US10513634B2 (en) 2019-12-24
TW201614019A (en) 2016-04-16
BR112017002560A2 (pt) 2017-12-05
CN106661409A (zh) 2017-05-10
DE102014217245A1 (de) 2016-03-03
MX2017001786A (es) 2017-05-23
US20170226382A1 (en) 2017-08-10
KR20170048387A (ko) 2017-05-08
CA2954937A1 (en) 2016-03-03
KR102009013B1 (ko) 2019-08-08
TWI658105B (zh) 2019-05-01

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